China won the fight against poverty in 2020 and then entered the post-poverty era tackling relative poverty. Farmers, migrant workers and poor groups in the urban system, as low-skilled labor force with lower level of technical skills, education or ability to cope with imbalance, constitute the three main target groups for poverty governance in the post-poverty era. They are exposed to relative poverty risk for lack of capability caused by institutional exclusion, the transformation of economic growth mode and their own limitations. The relative poverty of low-skilled labor force is ultimately attributed to the limitation of individual ability. In particular, lower level of skill leads to lower employment quality and thus they are unable to build sustainable livelihoods. To deal with relative poverty, it is necessary to promote skill formation from both static skills and dynamic skills and in two dimensions, i.e., skill width and skill depth. The employment quality can be improved to build sustainable livelihoods by way of vocational education, on-the-job training and national qualification framework supported by institutional guarantee and social cooperation mechanism guarantee.